Dynamic self-assembly and self-organized transport of magnetic micro-swimmers.

We demonstrate experimentally and in computer simulations that magnetic microfloaters can self-organize into various functional structures while energized by an external alternating (ac) magnetic field. The structures exhibit self-propelled motion and an ability to carry a cargo along a pre-defined path. The morphology of the self-assembled swimmers is controlled by the frequency and amplitude of the magnetic field.

Adsorption and Diffusion of Fluids in Defective Carbon Nanotubes: Insights from Molecular Simulations.

Single-walled carbon nanotubes (SWNTs) have been shown from both simulations and experiments to have remarkably low resistance to gas and liquid transport. This has been attributed to the remarkably smooth interior surface of pristine SWNTs. However, real SWNTs are known to have various defects that depend on the synthesis method and procedure used to activate the SWNTs. In this paper, we study adsorption and transport properties of atomic and molecular fluids in SWNTs having vacancy point defects. We construct models of defective nanotubes that have either unrelaxed defects, where the overall structure of the SWNT is not changed, or reconstructed defects, where the bonding topology and therefore the shape of the SWNT is allowed to change. Furthermore, we include partial atomic charges on the SWNT carbon atoms due to the reconstructed defects. We consider adsorption and diffusion of Ar atoms and CO2 and H2O molecules as examples of a noble gas, a linear quadrupolar fluid, and a polar fluid. Adsorption isotherms were found to be fairly insensitive to the defects, even for the case of water in the charged, reconstructed SWNT. We have computed both the self-diffusivities and corrected diffusivities (which are directly related to the transport diffusivities) for each of these fluids. In general, we found that at zero loading that defects can dramatically reduce the self- and corrected diffusivities. However, at high, liquidlike loadings, the self-diffusion coefficients for pristine and defective nanotubes are very similar, indicating that fluid-fluid collisions dominate the dynamics over the fluid-SWNT collisions. In contrast, the corrected diffusion coefficients can be more than an order of magnitude lower for water in defective SWNTs. This dramatic decrease in the transport diffusion is due to the formation of an ordered structure of water, which forms around a local defect site. It is therefore important to properly characterize the level and types of defects when accurate transport diffusivities are needed.

Spontaneous formation and nonequilibrium dynamics of a soliton-shaped Bose-Einstein condensate in a trap.

The Bose-stimulated self-organization of a quasi-two-dimensional nonequilibrium Bose-Einstein condensate in an in-plane potential is proposed. We obtained the solution of the nonlinear, driven-dissipative Gross-Pitaevskii equation for a Bose-Einstein condensate trapped in an external asymmetric parabolic potential within the method of the spectral expansion. We found that, in sharp contrast to previous observations, the condensate can spontaneously acquire a solitonlike shape for spatially homogeneous pumping. This condensate soliton performs oscillatory motion in a parabolic trap and, also, can spontaneously rotate. Stability of the condensate soliton in the spatially asymmetric trap is analyzed. In addition to the nonlinear dynamics of nonequilibrium Bose-Einstein condensates of ultracold atoms, our findings can be applied to the condensates of quantum well excitons and cavity polaritons in semiconductor heterostructure, and to the condensates of photons.

Designing Synthetic Microcapsules That Undergo Biomimetic Communication and Autonomous Motion.

Inspired by the collective behavior of slime molds and amoebas, we designed synthetic cell-like objects that move and self-organize in response to self-generated chemical gradients, thereby exhibiting autochemotaxis. Using computational modeling, we specifically focused on microcapsules that encompass a permeable shell and are localized on an adhesive surface in solution. Lacking any internal machinery, these spherical, fluid-filled shells might resemble the earliest protocells. Our microcapsules do, however, encase particles that can diffuse through the outer shell and into the surrounding fluid. The released particles play two important, physically realizable roles: (1) they affect the permeability of neighboring capsules and (2) they generate adhesion gradients on the underlying surface. Due to feedback mechanisms provided by the released particles, the self-generated adhesion gradients, and hydrodynamic interactions, the capsules undergo collective, self-sustained motion and even exhibit antlike tracking behavior. With the introduction of a chemically patterned stripe on the surface, a triad of capsules can be driven to pick up four-capsule cargo, transport this cargo, and drop off this payload at a designated site. We also modeled a system where the released particles give rise to a particular cycle of negative feedback loops (mimicking the "repressilator" network), which regulates the production of chemicals within the capsules and hence their release into the solution. By altering the system parameters, three capsules could be controllably driven to self-organize into a stable, close-packed triad that would either translate as a group or remain stationary. Moreover, the stationary triads could be made to switch off after assembly and thus produce minimal quantities of chemicals. Taken together, our models allow us to design a rich variety of self-propelled structures that achieve complex, cooperative behavior through fundamental physicochemical phenomena. The studies can also shed light on factors that enable individual protocells to communicate and self-assemble into larger communities.

Harnessing the polariton drag effect to design an electrically controlled optical switch.

We propose a design of a Y-shaped electrically controlled optical switch based on the studies of propagation of an exciton-polariton condensate in a patterned optical microcavity with an embedded quantum well. The polaritons are driven by a time-independent force due to the microcavity wedge shape and by a time-dependent drag force owing to the interaction of excitons in a quantum well and the electric current running in a neighboring quantum well. It is demonstrated that by applying the drag force one can direct more than 90% of the polariton flow toward the desired branch of the switch with no hysteresis. By considering the transient dynamics of the polariton condensate, we estimate the response speed of the switch as 9.1 GHz. We also propose a design of the polariton switch in a flat microcavity based on the geometrically identical Y-shaped quantum wells where the polariton flow is only induced by the drag force. The latter setup enables one to design a multiway switch that can act as an electrically controlled optical transistor with on and off functions. Finally, we performed the simulations for a microcavity with an embedded gapped graphene layer and demonstrated that in this case the response speed of the switch can be increased up to 14 GHz for the same switch size. The simulations also show that the energy gap in the quasiparticle spectrum in graphene can be utilized as an additional parameter that controls the propagation of the signals in the switch.

Wave turbulence in quantum fluids.

Wave turbulence (WT) occurs in systems of strongly interacting nonlinear waves and can lead to energy flows across length and frequency scales much like those that are well known in vortex turbulence. Typically, the energy passes although a nondissipative inertial range until it reaches a small enough scale that viscosity becomes important and terminates the cascade by dissipating the energy as heat. Wave turbulence in quantum fluids is of particular interest, partly because revealing experiments can be performed on a laboratory scale, and partly because WT among the Kelvin waves on quantized vortices is believed to play a crucial role in the final stages of the decay of (vortex) quantum turbulence. In this short review, we provide a perspective on recent work on WT in quantum fluids, setting it in context and discussing the outlook for the next few years. We outline the theory, review briefly the experiments carried out to date using liquid H2 and liquid (4)He, and discuss some nonequilibrium excitonic superfluids in which WT has been predicted but not yet observed experimentally. By way of conclusion, we consider the medium- and longer-term outlook for the field.

Fibers with integrated mechanochemical switches: minimalistic design principles derived from fibronectin.

Inspired by molecular mechanisms that cells exploit to sense mechanical forces and convert them into biochemical signals, chemists dream of designing mechanochemical switches integrated into materials. Using the adhesion protein fibronectin, whose multiple repeats essentially display distinct molecular recognition motifs, we derived a computational model to explain how minimalistic designs of repeats translate into the mechanical characteristics of their fibrillar assemblies. The hierarchy of repeat-unfolding within fibrils is controlled not only by their relative mechanical stabilities, as found for single molecules, but also by the strength of cryptic interactions between adjacent molecules that become activated by stretching. The force-induced exposure of cryptic sites furthermore regulates the nonlinearity of stress-strain curves, the strain at which such fibers break, and the refolding kinetics and fraction of misfolded repeats. Gaining such computational insights at the mesoscale is important because translating protein-based concepts into novel polymer designs has proven difficult.

Using mesoscopic models to design strong and tough biomimetic polymer networks.

Using computational modeling, we investigate the mechanical properties of polymeric materials composed of coiled chains, or "globules", which encompass a folded secondary structure and are cross-linked by labile bonds to form a macroscopic network. In the presence of an applied force, the globules can unfold into linear chains and thereby dissipate energy as the network is deformed; the latter attribute can contribute to the toughness of the material. Our goal is to determine how to tailor the labile intra- and intermolecular bonds within the network to produce material exhibiting both toughness and strength. Herein, we use the lattice spring model (LSM) to simulate the globules and the cross-linked network. We also utilize our modified Hierarchical Bell model (MHBM) to simulate the rupture and reforming of N parallel bonds. By applying a tensile deformation, we demonstrate that the mechanical properties of the system are sensitive to the values of N(in) and N(out), the respective values of N for the intra- and intermolecular bonds. We find that the strength of the material is mainly controlled by the value of N(out), with the higher value of N(out) providing a stronger material. We also find that, if N(in) is smaller than N(out), the globules can unfold under the tensile load before the sample fractures and, in this manner, can increase the ductility of the sample. Our results provide effective strategies for exploiting relatively weak, labile interactions (e.g., hydrogen bonding or the thiol/disulfide exchange reaction) in both the intra- and intermolecular bonds to tailor the macroscopic performance of the materials.

Modeling the nanoscratching of self-healing materials.

We use computational modeling to determine the mechanical response of crosslinked nanogels to an atomic force microscope (AFM) tip that is moved through the sample. We focus on two-dimensional systems where the nanogels are interconnected by both strong and labile bonds. To simulate this system, we modify the lattice spring model (LSM) to extend the applicability of this method to a broader range of elastic materials. Via this modified LSM, we model each nanogel as a deformable particle. We utilize the Bell model to describe the bonds between these nanogel particles, and subsequently, simulate the rupturing of bonds due to the force exerted by the moving indenter. The ruptured labile bonds can readily reform and thus can effectively mend the cavities formed by the moving AFM tip. We determine how the fraction of labile bonds, the nanogel stiffness, and the size and velocity of the moving tip affect the self-healing behavior of the material. We find that samples containing just 10% of labile bonds can heal to approximately 90% of their original, undeformed morphology. Our results provide guidelines for creating reconfigurable materials that can undergo self-repair and thereby withstand greater mechanical stress under everyday use.

Role of parallel reformable bonds in the self-healing of cross-linked nanogel particles.

We develop a hybrid computational approach to examine the mechanical properties and self-healing behavior of nanogel particles that are cross-linked by both stable and labile bonds. The individual nanogels are modeled via the lattice spring model (LSM), which is an effective method for probing the response of materials to mechanical deformation. The cross-links between the nanogels are simulated via the hierarchical Bell model (HBM), which allows us to capture the rupturing of multiple parallel bonds as the result of an applied force. Because the labile bonds are relatively reactive, they can reform after they have been ruptured. To incorporate the possibility of bonds reforming, we modify the HBM formalism and validate the modified HBM by considering a system of two surfaces, which are connected by multiple parallel bonds. We then use our hybrid HBM/LSM to simulate the behavior of the cross-linked nanogels under a tensile deformation. In these simulations, each labile linkage between the nanogels contains at most N parallel bonds. We vary the fraction of labile linkages and the value of N in these linkages to determine the optimal conditions for improving the robustness of the material. Although numerous parallel bonds within a linkage enhance the strength of the material, these bonds diminish the ductility and the ability of the material to undergo the structural rearrangements that are necessary for self-repair. For a relatively low fraction of labile bonds and N ≤ 4, however, we can significantly improve the strength of the material and preserve the self-healing properties. For instance, a sample with 30% labile linkages and N = 4 per linkage is roughly 200% stronger than a sample that is cross-linked solely by stable bonds and can still undergo self-repair in response to the tensile deformation. The results reveal how mechanical stress can lead not only to the appearance of cavities within the material but also to bond formation that "heals" these cavities and thus prevents the catastrophic failure of the material.

Designing communicating colonies of biomimetic microcapsules.

Using computational modeling, we design colonies of biomimetic microcapsules that exploit chemical mechanisms to communicate and alter their local environment. As a result, these synthetic objects can self-organize into various autonomously moving structures and exhibit ant-like tracking behavior. In the simulations, signaling microcapsules release agonist particles, whereas target microcapsules release antagonist particles and the permeabilities of both capsule types depend on the local particle concentration in the surrounding solution. Additionally, the released nanoscopic particles can bind to the underlying substrate and thereby create adhesion gradients that propel the microcapsules to move. Hydrodynamic interactions and the feedback mechanism provided by the dissolved particles are both necessary to achieve the collective dynamics exhibited by these colonies. Our model provides a platform for integrating both the spatial and temporal behavior of assemblies of "artificial cells," and allows us to design a rich variety of structures capable of exhibiting complex, cooperative behavior. Due to the cell-like attributes of polymeric microcapsules and polymersomes, material systems are available for realizing our predictions.

Using nanoparticle-filled microcapsules for site-specific healing of damaged Substrates: creating a "repair-and-go" system.

Using a hybrid computational approach, we simulate the behavior of nanoparticle-filled microcapsules that are propelled by an imposed shear to move over a substrate, which encompasses a microscopic crack. When the microcapsules become localized in the crack, the nanoparticles can penetrate the capsule's shell to bind to and fill the damaged region. Initially focusing on a simple shear flow, we isolate conditions where the microcapsules become arrested in the cracks and those where the capsules enter the cracks for a finite time but are driven to leave this region by the imposed flow. We also characterize the particle deposition process for these two scenarios, showing that the deposition is greater for the arrested capsules. We then determine the effect of utilizing a pulsatile shear flow and show that this flow field can lead to an effective "repair-and-go" system where the microcarriers not only deliver a high volume fraction of particles into the crack but also leave the fissure and, thus, can potentially repair additional damage within the system.

Harnessing labile bonds between nanogel particles to create self-healing materials.

Using computational modeling, we demonstrate the self-healing behavior of novel materials composed of nanoscopic gel particles that are interconnected into a macroscopic network by both stable and labile bonds. Under mechanical stress, the labile bonds between the nanogels can break and readily re-form with reactive groups on neighboring units. This breaking and re-forming allows the units in the network to undergo a structural rearrangement that preserves the mechanical integrity of the sample. The simulations show that just a small fraction of labile bonds leads to a roughly 25% increase in the stress needed to induce fracture. Thus, the labile bonds can significantly improve the tensile strength of the material. The findings provide guidelines for creating high-strength, self-healing materials.